Acridine vat dyes



United fitates ACRIDINE VAT DYES William Baptist Hardy, Bound Brook, N. J., and Oscar George Birsten, NewYork, N. Y., assignors to American Cyanamid Company, New York, N. Y. a corporation of Maine t No Drawing. Application December 17, 1956 Serial No. 628,496

Claims. (Cl. 260-274) This invention relates to new acridine vat dyes, and more particularly to 16 H-isothiazolo[5',4,3',5,10] anthra[2,l,9-mna]-napth[2,3-hlacridine-lO,l5-dione 4,4- dioxide have the basic ring structure:

This application is a continuation-in-part of our application Serial Number 448,754, filed August 9, 1954, and now Patent Number 2,799,682, entitled 5(S)10(N)isothiazolobenzanthracenedioxides.

Quinone sulfimines having the structures and the corresponding naphthoquinone and anthraquinone derivatives, have recently been described by Adams et al. in a series of articles appearing in the Journal of the American Chemical Society. These compounds are very Sensitive to alkali, losing sulfonic acid and ammonia when heated with strong alkali. Consequently, such compounds-are useless in the preparation of fused ring systems of the benzanthrone type where alkali fusion to produce such ring systems is required.

Thepresent invention is based upon the discovery that a somewhat analogous cyclic structure in which the S0 groupis ring closed into the anthraquinone system is stable to akali fusion and is highly useful in the preparation of condensed ring systems needed for the deep shades of vat dyes. We have found that the isothiazolodioxide ring system, as described more particularly hereinafter, may be used to prepare a benzanthrone analog by the atent Q The preparation of the intermediates may be carried out by first treating l(S)9(N)isothiazoloanthraquinonedioxide of the structure 0,sN which may be prepared by the method of Ullmann and Kertesz [Ben 52, 545 (1919)], with glycerin, sulfuric acid and a reducing metal in the standard benzanthrone condensation to produce 5(S)10(N)isothiazolobenzanthracenedioxide of the structure The numbering system used is shown in the above formula. For convenience, double bonds are not shown, where the location is obvious. It is believed that this is the correct structure because it is highly unlikely that the formation of the new ring would occur by ring closure into a ring already substituted by a sulfonyl group, especially when an unsubstituted ring 'is equally available. However, this point is not certain and we do not wish to be limited thereby.

The basic ring system could also be named as 5(3) 10(N) isothiazolobenzanthronedioxide, or by the Chemical Abstracts system as benzonaphthenoll,2,3,-cd] [1,2] benzisothiazole 2,2-dioxide or phenaleno[l,2,3,-cdl[1,2] benzisothiazole 2,2-dioxide:

NSO2

By a frequently used oxa-aza system, the name would be 2-thia-1-aza-2H-benz [h,i] aceanthrylene-2,Z-dioxide. The characteristics of the compound are accentuated by naming the compound as an isothiazolobenzanthracenedioro ide, and such terminology is used elsewhere in this specification.

The isothiazolobenzanthracenedioxide can be brominated in acetic acid to produce Bz-1-bromo-5(S)10(l l) Bromination of the dagsaesea s thiazqlobeuzanthracenedio ide- Ch rina io at this isothiazolobenzanthronedioxide can also be carried out to give the related chloro compounds, although the bromin compounds e pre erre hey re ct m e ead ly: with m pamhraq uones E en a. large xc ss. i tq ine isfcund o i a, mouor rcrun deriua ive- By a a o y- With the h omina i a Q benzanthrone such sub i ution s n al p ba i ty a he Zrl pos tion.

The intermediates can be readily condensed with amino-v en h aquiu nc t i aa lu mides; hich may en be in clo ed; by fusiqn n 1 Po assi m hy roxide methanol mix re. to produ e cr d u r en dyes.

' Va us ubs ituted. ,a i an au hraqu ncns may be. used to form the anthrimides, ,Exarnples; of such, amino; anthr q in ne re i-amino:4-benzat idoranthraqu on l-aminor l-me hcxy. anthraqu ng e, 1raIniu :6.-methoxyanthraquinone, and the like. In somefirstances-thesube stituent group in the aminoanthraquinone may be attacked during the ring closure by fusion in a potassium hydroxide methanol mixture. Forexample, in the case of alkoxy derivatives, some dealkylation usually takes place under theconditions used. However, if it is desired that the final dye retain the alko'xy group, the dealkylated material maybe realkylated after the ring closure fusion. Again, benzamido groups are usually cleaved during the closure of the acridine ring; the resultant free amino compound can be after-acylatedjor allgylated; i I

These re ctions are believed to go through the, followc e e s g, he-am saal w e r Pm.- poses of illustration.

The isothiazolobenzanthracenedioxide can also be nitrated. Reduction of the nitro compound with ferrous sulfate and ammonia readily; giyes the aminoderivative. This too may be condensed with halogenoanthraquinones to give anthrirnides similar to.those,preparedxfromihq bromo substituted isothjazolobenzauthronedioxide.t

I The 5 (S) (N)isothiazolobenzanthracenedioxide vralso may. (be prepared with, substitutents in the ring.- Thus, for example, BZ-Z-methyL and Bz 2aphenyl'.derivatives;

can be prepared by the use of methacrolein and Z-phenylt- F acrolein, respectively,=instead of'glycerin or-acroleimin thestandard bQHZaHthIODe SYIHhBSiS;

' watergaudg5;g t r-concentr tedhy rochlor c Also, the isothiazoloanthraquinonedioxide may he. prep-l pared from substituted anthraquinones, as, for example, when 1-sulfo-2-rnethylanthraqui1ione is used, an isothiazolobenzanthracenedioxide is obtained in'which a methyl group is ortho to the su l l'. 0n the 6 position in the ring; In a similar manner isothiazolobenzanthracenedioxides with substituents in the anthraquinone ring may be prepared by using I-sul-foanthraquinones containingsubSt-ie tueuts such as; allgoxwarylo ya carh xy; nit-to: audhalos in. positions 3., 4, 6",. '7: or-8' and? sucliihte'rmediateszi used for preparation of the present dyes. g j

The: inven i n will. be. described ingreater. detail in conjunction with the following; specific examples in which the parts are by weightunless otherwise specified.

EXAMPLE; 1%

A mixture of 5.4 parts of,1 (5)9(N3isothiazoloanthraquinonedioxide, 3.1 parts of glyc'erin, 1.2 parts of hydrated copper, sulfate, and 6.1 parts of watertis stirred while 51.9 parts of concentrated sulfuric: acid'are added, the temperature being keptbelow C. The mixture isthen heated to 105 C. and 1.9 astor zinc dust are added gradually at this temperature, Thenmixturer, is

' therrdrowned and the" productfisfisolated by filtration.

The filter cake is =tho'roughly. extracted with dildtefsodi hydroxide solution at 'roomtemperaturej after which the? product is filtered, washedfj'and'dfiedfi Itis""-aldark" greenish-yellow solidwhich do'es not vat and" does not melt below 320 C. It is insolfuble in most organic solvents but slightly soluble in boiling nitrobenzene.

EXAMBLEZ Five parts of theproduct-,of Examplevl are: issplved in parts ofi sulfuric 'acidfand- -the mixture, drowned ic s-R fg ct fil ed; di washedc d fle s heur l ri d iuz am xture ch30 parts 01.5 A

) e301 p rt 'o ce idestrpyed with his. atioua=washing.-iandedw .ing; It; is grecr-ystallizedz from;znitrqhenzene tandsgiy good-analysis for-1a monobromoisothiazolobenzanthracen dioxide; It is .aohservedr to havea' a v. meltingiipoiut EXAMPLE 3 A mixture of 2.1 parts of the product of Example 2, 1.3 parts of alpha-aminoanthraquinone, 0.2 part of powdered copper, 0.2 part of iodine, 3 parts of anhydrous potassium carbonate, and 36 parts of nitrobenzcne'is stirred at 210 C. until the reaction is substantially complete. The mixture is then cooled to room temperature and the precipitated product is filtered and washed with nitrobenzene and alcohol. It is then slurried in dilute hydrochloric acid and the final product is isolated by filtration and washing.

EXAMPLE 4 1 6H -isthiaz0l0 ',4',3 ',5 ,1 0] anthra [2,] .9-mna] naphth [2,3-h]-acridine-10,15-dione 4 ,4-di0xide EXAMPLE 5 l OCH:

ozhll 4 separated by extraction with an alkaline reagent.

The procedure of Example 3 is followed except that an equivalent amount of l-amino-4-methoxy anthroquinone is used in place of the l-aminoanthraquinone. The product of the above formula is obtained.

EXAMPLE 6 Ring closure of the product of Example 5 is effected using a procedure similar to that described in Example 4. The product which is formed contains some hydroxy compound which results from the dealkylation of ,the methoxy group. The demethylated product may be The demethylated product may be reconverted to the methyl,- ated product if desired by methylation with dimethyl sulfate.

EXAMPLE 7 OzSN The procedure of Example 3 is followed except that an equivalent quantity of 4-benzamido-l-aminoanthraquinone is used in place of the l-aminoanthraquinone.

EXAMPLE 8 Gas-N Ring closure of the product of Example 7 is efiected hyrreactiomwith potassium hydroxide in'me'thanol. using 4. The dyestufi of the-:stru the iprocedur e described in Example A; The product v which isiobtaipectafromdhering closure is the tree amino product, since thewben zamido gmupJis-hydmlyzed- 11ming the ring closure fusiqn 5" We claim:

2. The dyestufflof the structure 0,sXN-

5.: Thei-dyestufiiof the -structure:-

r s --wpr v in which. R represents a member of the group consisting of hydrogeu, CH 0-'--, and I 3; The-dyestufief the structure Gash-N N01 references cited. 

2. THE DYESTUFF OF THE STRUCTURE 